Abstract
Synthesis of stereodefined carbocyclic and heterocyclic tertiary boronic esters is accomplished by performing a conjunctive cross-coupling reaction on preformed cyclic boron ate complexes. Boronates bearing spirocyclic and aryl bicyclic skeletons can be synthesized enantioselectively using a chiral PHOX-ligated Pd catalyst with achiral starting material, while substrates bearing continuous stereogenic centers can be generated diastereoselectively. A variety of aryl and alkenyl electrophiles are incorporated.